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While the room temperature reaction of [RuCl 2 (CO) 3 ] 2  and Ph 2 S in tetrahydrofuran in air affords [RuCl 2 (CO) 2 (SPh 2 ) 2 ] (1) in moderate yield, that in dichloromethane results in the formation of a mixture of [RuCl 2 (CO) 3 (H 2 O)] (2) and [Ru(H 2 O) 6 ][RuCl 3 (CO) 3 ] 2 ·2H 2 O (3). Very small amounts of 1 are produced only upon prolonged reflux of the reagents. All compounds were characterized by X-ray crystallography. 1 crystallizes as discrete octahedral cis(CO), cis(Cl), trans(Ph 2 S) complexes, which are joined into stacks by weak H···Cl hydrogen bonds. 2 is also composed of discrete octahedral complexes. Four hydrogen bonds involving aqua and chlorido ligands link two complexes into a dimer. The structure of 3 consists of octahedral hexaaquaruthenium cations and two tricarbonyltrichloridoruthenate anions. The water of crystallization is involved in hydrogen bonding between the cations and anions resulting in the formation of a continuous three-dimensional network.

Formation and Structural Characterization of [RuCl 2 (CO) 2 (SPh 2 ) 2 ], [RuCl 2 (CO) 3 (OH 2 )], and [Ru(OH 2 ) 6 ][RuCl 3 (CO) 3 ] 2 · 2H 2 O